CN114551868B - Negative electrode material of sodium ion battery and preparation method thereof - Google Patents
Negative electrode material of sodium ion battery and preparation method thereof Download PDFInfo
- Publication number
- CN114551868B CN114551868B CN202210098304.0A CN202210098304A CN114551868B CN 114551868 B CN114551868 B CN 114551868B CN 202210098304 A CN202210098304 A CN 202210098304A CN 114551868 B CN114551868 B CN 114551868B
- Authority
- CN
- China
- Prior art keywords
- copper
- ion battery
- vanadium
- sodium ion
- source
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 31
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000010405 anode material Substances 0.000 claims abstract description 22
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 19
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 239000011593 sulfur Substances 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 4
- MFWFDRBPQDXFRC-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;vanadium Chemical compound [V].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MFWFDRBPQDXFRC-LNTINUHCSA-N 0.000 claims description 13
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 12
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- -1 copper fluoroborate Chemical compound 0.000 claims description 6
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 6
- 235000018417 cysteine Nutrition 0.000 claims description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 4
- 239000005750 Copper hydroxide Substances 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 4
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 3
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 claims description 3
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims description 3
- 229940116318 copper carbonate Drugs 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- YRNNKGFMTBWUGL-UHFFFAOYSA-L copper(ii) perchlorate Chemical compound [Cu+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O YRNNKGFMTBWUGL-UHFFFAOYSA-L 0.000 claims description 3
- PUHAKHQMSBQAKT-UHFFFAOYSA-L copper;butanoate Chemical compound [Cu+2].CCCC([O-])=O.CCCC([O-])=O PUHAKHQMSBQAKT-UHFFFAOYSA-L 0.000 claims description 3
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 3
- LLVVIWYEOKVOFV-UHFFFAOYSA-L copper;diiodate Chemical compound [Cu+2].[O-]I(=O)=O.[O-]I(=O)=O LLVVIWYEOKVOFV-UHFFFAOYSA-L 0.000 claims description 3
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 claims description 3
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000001351 cycling effect Effects 0.000 abstract description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 15
- 229910052708 sodium Inorganic materials 0.000 description 15
- 239000011734 sodium Substances 0.000 description 15
- 238000005303 weighing Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 238000011056 performance test Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 2
- VJNMUKGZDONIAN-UHFFFAOYSA-N 1-methylisoquinolin-6-amine Chemical compound NC1=CC=C2C(C)=NC=CC2=C1 VJNMUKGZDONIAN-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 1
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 description 1
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 description 1
- QKDGGEBMABOMMW-UHFFFAOYSA-I [OH-].[OH-].[OH-].[OH-].[OH-].[V+5] Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[V+5] QKDGGEBMABOMMW-UHFFFAOYSA-I 0.000 description 1
- KSECJOPEZIAKMU-UHFFFAOYSA-N [S--].[S--].[S--].[S--].[S--].[V+5].[V+5] Chemical compound [S--].[S--].[S--].[S--].[S--].[V+5].[V+5] KSECJOPEZIAKMU-UHFFFAOYSA-N 0.000 description 1
- IBJKCMMJJCJCLT-UHFFFAOYSA-M [S-2].[S-2].[SH-].[V+5] Chemical compound [S-2].[S-2].[SH-].[V+5] IBJKCMMJJCJCLT-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- HHQFLEDKAVLHOM-UHFFFAOYSA-N oxovanadium;trihydrofluoride Chemical compound F.F.F.[V]=O HHQFLEDKAVLHOM-UHFFFAOYSA-N 0.000 description 1
- NFVUDQKTAWONMJ-UHFFFAOYSA-I pentafluorovanadium Chemical compound [F-].[F-].[F-].[F-].[F-].[V+5] NFVUDQKTAWONMJ-UHFFFAOYSA-I 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- AAWFOGYSSVYINI-UHFFFAOYSA-K triiodovanadium Chemical compound I[V](I)I AAWFOGYSSVYINI-UHFFFAOYSA-K 0.000 description 1
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 description 1
- JTWLHYPUICYOLE-UHFFFAOYSA-J vanadium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[V+4] JTWLHYPUICYOLE-UHFFFAOYSA-J 0.000 description 1
- WSJLOGNSKRVGAD-UHFFFAOYSA-L vanadium(ii) bromide Chemical compound [V+2].[Br-].[Br-] WSJLOGNSKRVGAD-UHFFFAOYSA-L 0.000 description 1
- ZOYIPGHJSALYPY-UHFFFAOYSA-K vanadium(iii) bromide Chemical compound [V+3].[Br-].[Br-].[Br-] ZOYIPGHJSALYPY-UHFFFAOYSA-K 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- 229940041260 vanadyl sulfate Drugs 0.000 description 1
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/006—Compounds containing, besides copper, two or more other elements, with the exception of oxygen or hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a sodium ion battery anode material which is spherical Cu 3VS4. The invention also discloses a preparation method of the sodium ion battery anode material, which comprises the steps of adding a vanadium source, a copper source and a sulfur source into a methanol solvent for reaction at 160-220 ℃, and obtaining the sodium ion battery anode material when the reaction reaches an environment with excessive vanadium source, wherein the sodium ion battery anode material is spherical Cu 3VS4. The negative electrode material has excellent cycling stability under high current density, and the preparation method is simple and low in cost.
Description
Technical Field
The invention relates to a battery negative electrode material and a preparation method thereof, in particular to a sodium ion battery negative electrode material and a preparation method thereof.
Background
As an important energy storage device, lithium ion batteries are attracting attention due to their advantages of high operating voltage, high energy density, long cycle life, low self-discharge rate, no memory effect, environmental protection, etc. At present, with the rapid development of the new energy automobile industry, the demand for lithium ion batteries is increasing. However, global lithium resources are scarce and large-scale applications are difficult to realize.
Compared with a lithium ion battery, the sodium ion battery has the advantages that sodium resources are more abundant and cheaper, and sodium ions have similar chemical properties with lithium ions, so that the sodium ion battery can replace the lithium ion battery to become a main energy storage device of the next generation. However, the electrochemical performance of the sodium ion battery is affected by slower migration of sodium ions due to larger ionic radius during operation of the sodium ion battery. Among them, the electrode material is a key component of the sodium ion battery, and the performance of the electrode material directly affects the performance of the sodium ion battery, so it is important to develop the electrode material with excellent electrochemical performance.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention aims to provide a negative electrode material for a sodium ion battery, which aims to solve the problems that the existing drawbacks of the sodium ion battery, especially the long-term cycling stability of the electrode material under high current density is difficult to realize due to the large radius of sodium ions. The invention further aims at providing a preparation method of the negative electrode material of the sodium ion battery.
The technical scheme of the invention is as follows: a negative electrode material of a sodium ion battery is spherical Cu 3VS4.
Further, the diameter of the spherical Cu 3VS4 is 1-2 μm.
The preparation method of the sodium ion battery cathode material comprises the steps of adding a vanadium source, a copper source and a sulfur source into a methanol solvent for reaction at 160-220 ℃, and obtaining the sodium ion battery cathode material when the reaction is carried out to reach an environment with excessive vanadium source, wherein the sodium ion battery cathode material is spherical Cu 3VS4.
Further, the vanadium source is one or more of vanadium acetylacetonate, vanadium oxide, vanadate and vanadium-containing halide.
Further, the copper source is a copper salt, and the copper salt is one or more of copper sulfate, copper chloride, copper nitrate, copper hydroxide, copper citrate, copper fluoroborate, copper acetate, copper iodate, copper carbonate, copper butyrate, copper oxalate, copper phosphate, copper perchlorate and copper tetrafluoroborate.
Further, the sulfur source is one or more of thioacetamide, thiourea and cysteine.
Further, the reaction time is 12 to 72 hours.
Further, the molar ratio of the vanadium source to the sulfur source is 1:0.5-1:2, and the molar ratio of the vanadium source to the copper source is 1:0.1-1:0.5.
Compared with the prior art, the invention has the advantages that:
The spherical Cu 3VS4 anode material has extremely large specific surface area, is favorable for infiltration of electrolyte, remarkably increases the contact area between the electrolyte and the electrode surface, provides more reactive sites, can buffer the volume change in the charge and discharge process of the electrode material, prevents the agglomeration of Cu 3VS4, and is favorable for ensuring the structural integrity of the sphere, thereby improving the stability of the cycle performance of the spherical Cu 3VS4. The preparation method disclosed by the invention is simple to operate, simple in steps and low in preparation cost.
Drawings
FIG. 1 is an X-ray diffraction chart of example 1 of the present invention.
FIG. 2 is a scanning electron microscope (low magnification) of example 1 of the present invention.
FIG. 3 is a scanning electron microscope (high magnification) of example 1 of the present invention.
Fig. 4 is a cycle performance chart of the half cell of example 1 of the present invention.
Detailed Description
The invention is further illustrated, but is not limited, by the following examples.
The preparation method of the sodium ion battery cathode material comprises the steps of adding a copper source, a sulfur source and an excessive vanadium source into a methanol solvent for reaction, wherein the vanadium source is one or more of vanadium acetylacetonate, vanadium oxide, vanadate and vanadium-containing halide, and can be specifically one or more of vanadium acetylacetonate, vanadium pentoxide, sodium vanadate, vanadium peroxo acid, vanadyl sulfate, orthovanadate, ammonium metavanadate, vanadium dioxide, vanadium dibromide, vanadium dioxide, sodium metavanadate, vanadium hydroxide, vanadium triiodide, vanadium trifluoride, vanadyl trifluoride, vanadium trisulfide, vanadium trichloride, vanadium trioxide, vanadium tetrafluoride, vanadium tetrachloride, vanadium pentafluoride and vanadium pentasulfide. The copper source is one or more of copper sulfate, copper chloride, copper nitrate, copper hydroxide, copper citrate, copper fluoroborate, copper acetate, copper iodate, copper carbonate, copper butyrate, copper oxalate, copper phosphate, copper perchlorate and copper tetrafluoroborate. The sulfur source is one or more of thioacetamide, thiourea and cysteine.
Example 1
Accurately weighing 1.4g of vanadium acetylacetonate, 0.3g of thioacetamide and 0.16g of copper nitrate trihydrate, adding into 35mL of methanol, magnetically stirring for 5min at a rotating speed of 500r/min, transferring into a 50mL reaction kettle, reacting for 24h at 200 ℃, washing and drying to obtain the Cu 3VS4 anode material with the spherical structure.
FIG. 1 is an X-ray diffraction pattern of the product obtained in this example, and all of the X-ray powder diffraction peaks can be indexed as Cu 3VS4. FIG. 2 is a low-magnification scanning electron micrograph of the product obtained in this example, from which it can be seen that the sample obtained in this example has a spherical structure (1-2 μm). FIG. 3 is a high-magnification scanning electron micrograph of the product obtained in this example, from which it can be seen that the spherical structure of the sample obtained in this example is roughened. the product obtained in the example of fig. 4 has a half-cell cycle graph of sodium sheet, and has a capacity of 274mah g -1 after 25000 cycles at a high current density of 20A g -1, and a capacity retention rate of 87%, and shows excellent cycle stability.
Example 2
Accurately weighing 0.37g of vanadium pentoxide, 0.3g of thiourea and 0.05g of copper chloride, adding into 35mL of methanol, magnetically stirring for 5min at a rotating speed of 500r/min, transferring into a 50mL reaction kettle, and reacting for 24h at 200 ℃. And standing and washing the collected sample for three times to obtain the Cu 3VS4 anode material with the spherical structure. The obtained material is used for carrying out electrochemical performance test on a half cell of a sodium sheet, and still has the capacity of 251mAh g -1 after 20000 times of circulation under the high current density of 20A g -1.
Example 3
Accurately weighing 1.4g of vanadium acetylacetonate, 0.3g of thioacetamide and 0.16g of copper nitrate trihydrate, adding into 35mL of methanol, magnetically stirring for 5min at a rotating speed of 500r/min, transferring into a 50mL reaction kettle, reacting for 24h at 160 ℃, washing and drying to obtain the Cu 3VS4 anode material with the spherical structure. The obtained material is used for carrying out electrochemical performance test on a half cell of a sodium sheet, and still has 269mAh g -1 capacity after 20000 cycles at a high current density of 20A g -1.
Example 4
Accurately weighing 1.4g of vanadium acetylacetonate, 0.3g of thioacetamide and 0.16g of copper nitrate trihydrate, adding into 35mL of methanol, magnetically stirring for 5min at a rotating speed of 500r/min, transferring into a 50mL reaction kettle, reacting for 24h at 220 ℃, washing and drying to obtain the Cu 3VS4 anode material with the spherical structure. The obtained material is used for carrying out electrochemical performance test on a half cell of a sodium sheet, and still has the capacity of 240mAh g -1 after 20000 times of circulation under the high current density of 20A g -1.
Example 5
Accurately weighing 1.4g of vanadium acetylacetonate, 0.3g of thioacetamide and 0.16g of copper nitrate trihydrate, adding into 35mL of methanol, magnetically stirring for 5min at a rotating speed of 500r/min, transferring into a 50mL reaction kettle, reacting for 12h at 200 ℃, washing and drying to obtain the Cu 3VS4 anode material with the spherical structure. The obtained material is used for carrying out electrochemical performance test on a half cell of a sodium sheet, and the capacity of 242mAh g -1 still exists after 20000 times of circulation under the high current density of 20A g -1.
Example 6
Accurately weighing 1.4g of vanadium acetylacetonate, 0.3g of thioacetamide and 0.16g of copper nitrate trihydrate, adding into 35mL of methanol, magnetically stirring for 5min at a rotating speed of 500r/min, transferring into a 50mL reaction kettle, reacting for 72h at 200 ℃, washing and drying to obtain the Cu 3VS4 anode material with the spherical structure. The obtained material is used for carrying out electrochemical performance test on a half cell of a sodium sheet, and the capacity of 249mAh g -1 still exists after 20000 times of circulation under the high current density of 20A g -1.
Example 7
Accurately weighing 1.4g of vanadium acetylacetonate, 0.6g of thioacetamide and 0.16g of copper nitrate trihydrate, adding into 35mL of methanol, magnetically stirring for 3min at a rotating speed of 500r/min, transferring into a 50mL reaction kettle, and reacting for 24h at 200 ℃. And standing and washing the collected sample for three times to obtain the Cu 3VS4 anode material with the spherical structure. The obtained material is used for carrying out electrochemical performance test on a half cell of a sodium sheet, and still has the capacity of 252mAh g -1 after 20000 times of circulation under the high current density of 20A g -1.
Example 8
Accurately weighing 1.4g of vanadium acetylacetonate, 0.15g of thioacetamide and 0.16g of copper nitrate trihydrate, adding into 35mL of deionized water, magnetically stirring for 10min at a rotating speed of 300r/min, transferring into a 50mL reaction kettle, and reacting for 24h at 200 ℃. And standing and washing the collected sample for three times to obtain the Cu 3VS4 anode material with the spherical structure. The obtained material is used for carrying out electrochemical performance test on a half cell of a sodium sheet, and still has 261mAh g -1 capacity after 25000 times of circulation under the high current density of 20A g -1.
Example 9
Accurately weighing 1.4g of vanadium acetylacetonate, 0.3g of thioacetamide and 0.1g of copper nitrate trihydrate, adding into 35mL of deionized water, magnetically stirring for 10min at a rotating speed of 300r/min, transferring into a 50mL reaction kettle, and reacting for 24h at 200 ℃. And standing and washing the collected sample for three times to obtain the Cu 3VS4 anode material with the spherical structure. The obtained material is used for carrying out electrochemical performance test on a half cell of a sodium sheet, and the capacity of 266mAh g -1 still exists after 25000 times of circulation under the high current density of 20A g -1.
Example 10
Accurately weighing 1.4g of vanadium acetylacetonate, 0.3g of thioacetamide and 0.5g of copper nitrate trihydrate, adding into 35mL of deionized water, magnetically stirring for 10min at a rotating speed of 300r/min, transferring into a 50mL reaction kettle, and reacting for 24h at 200 ℃. And standing and washing the collected sample for three times to obtain the Cu 3VS4 anode material with the spherical structure. The obtained material is used for carrying out electrochemical performance test on a half cell of a sodium sheet, and still has capacity of 259mAh g -1 after 25000 times of circulation under high current density of 20A g -1.
Example 11
Accurately weighing 0.33g of vanadium dioxide, 0.48g of cysteine and 0.07g of copper hydroxide, adding into 35mL of deionized water, magnetically stirring for 10min at a rotating speed of 300r/min, transferring into a 50mL reaction kettle, and reacting for 24h at 200 ℃. And standing and washing the collected sample for three times to obtain the Cu 3VS4 anode material with the spherical structure. The obtained material is used for carrying out electrochemical performance test on a half cell of a sodium sheet, and the capacity of 257mAh g -1 still exists after 20000 times of circulation under the high current density of 20A g -1.
Example 12
Accurately weighing 1.16g of vanadium tribromide, 0.48g of cysteine and 0.11g of copper sulfate, adding into 35mL of deionized water, magnetically stirring for 10min at a rotating speed of 300r/min, transferring into a 50mL reaction kettle, and reacting for 24h at 200 ℃. And standing and washing the collected sample for three times to obtain the Cu 3VS4 anode material with the spherical structure. The obtained material is used for carrying out electrochemical performance test on a half cell of a sodium sheet, and the capacity of 264mAh g -1 still exists after 20000 times of circulation under the high current density of 20A g -1.
Example 13
Accurately weighing 0.47g of ammonium metavanadate, 0.48g of cysteine and 0.11g of copper sulfate, adding into 35mL of deionized water, magnetically stirring for 10min at a rotating speed of 300r/min, transferring into a 50mL reaction kettle, and reacting for 24h at 200 ℃. And standing and washing the collected sample for three times to obtain the Cu 3VS4 anode material with the spherical structure. The obtained material is used for carrying out electrochemical performance test on a half cell of a sodium sheet, and still has a capacity of 260mAh g -1 after 20000 cycles at a high current density of 20A g -1.
Comparative example 1
Accurately weighing 0.635g of elemental copper, 1.02g of elemental vanadium and 1.12g of sulfur powder, mixing together, and grinding in a mortar. The mixture was then sealed in a quartz tube at vacuum <10 -4 mbar. Heating to 600 ℃ at a heating rate of 100 ℃/h, preserving heat for 24 hours, and then heating to 850 ℃ and preserving heat for 5 days to obtain the pure-phase CuV 2S4 anode material. The obtained material is used for carrying out electrochemical performance test on a half cell of a sodium sheet, and can reach the capacity of 230mAh g -1 under the high current density of 20A g -1.
Claims (5)
1. The preparation method of the sodium ion battery anode material is characterized in that a vanadium source, a copper source and a sulfur source are added into a methanol solvent for reaction at 160-220 ℃, and the environment of excessive vanadium source is achieved during the reaction, so that the sodium ion battery anode material is obtained, the sodium ion battery anode material is spherical Cu 3VS4, the diameter of the spherical Cu 3VS4 is 1-2 mu m, the molar ratio of the vanadium source to the sulfur source is 1:0.5-1:2, and the molar ratio of the vanadium source to the copper source is 1:0.1-1:0.5.
2. The method for preparing a negative electrode material of a sodium ion battery according to claim 1, wherein the vanadium source is one or more of vanadium acetylacetonate, vanadium oxide, vanadate and vanadium-containing halide.
3. The method for preparing a negative electrode material of a sodium ion battery according to claim 1, wherein the copper source is copper salt, and the copper salt is one or more of copper sulfate, copper chloride, copper nitrate, copper hydroxide, copper citrate, copper fluoroborate, copper acetate, copper iodate, copper carbonate, copper butyrate, copper oxalate, copper phosphate, copper perchlorate and copper tetrafluoroborate.
4. The method for preparing a negative electrode material of a sodium ion battery according to claim 1, wherein the sulfur source is one or more of thioacetamide, thiourea and cysteine.
5. The method for preparing a negative electrode material for a sodium ion battery according to claim 1, wherein the reaction time is 12 to 72 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210098304.0A CN114551868B (en) | 2022-01-27 | 2022-01-27 | Negative electrode material of sodium ion battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210098304.0A CN114551868B (en) | 2022-01-27 | 2022-01-27 | Negative electrode material of sodium ion battery and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114551868A CN114551868A (en) | 2022-05-27 |
| CN114551868B true CN114551868B (en) | 2024-04-19 |
Family
ID=81674050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210098304.0A Active CN114551868B (en) | 2022-01-27 | 2022-01-27 | Negative electrode material of sodium ion battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114551868B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102031565A (en) * | 2010-10-15 | 2011-04-27 | 中国科学院安徽光学精密机械研究所 | Polycrystal material with sulvanite structure and application thereof |
| JP2018058732A (en) * | 2016-10-06 | 2018-04-12 | 三井化学株式会社 | PROCESS FOR PRODUCING COPPER VANADIUM SULFIDE, PHOTOCATALYST AND COCATALYST-CARRYING Cu3VS4 |
| CN108993541A (en) * | 2018-09-10 | 2018-12-14 | 重庆第二师范学院 | A kind of photochemical catalyst Cu3VS4Preparation method |
| CN109599560A (en) * | 2018-12-11 | 2019-04-09 | 广东工业大学 | Four vanadic sulfide anode material of lithium-ion batteries of one kind and preparation method thereof |
| CN109761277A (en) * | 2019-01-17 | 2019-05-17 | 广东工业大学 | One kind five aoxidizes three vanadium negative electrode materials, preparation method and applications |
| CN109775759A (en) * | 2019-01-10 | 2019-05-21 | 广东工业大学 | A kind of vanadium dioxide anode material of lithium-ion battery and preparation method thereof |
| CN113912023A (en) * | 2021-10-08 | 2022-01-11 | 常熟理工学院 | Preparation method of sodium ion battery negative electrode material |
-
2022
- 2022-01-27 CN CN202210098304.0A patent/CN114551868B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102031565A (en) * | 2010-10-15 | 2011-04-27 | 中国科学院安徽光学精密机械研究所 | Polycrystal material with sulvanite structure and application thereof |
| JP2018058732A (en) * | 2016-10-06 | 2018-04-12 | 三井化学株式会社 | PROCESS FOR PRODUCING COPPER VANADIUM SULFIDE, PHOTOCATALYST AND COCATALYST-CARRYING Cu3VS4 |
| CN108993541A (en) * | 2018-09-10 | 2018-12-14 | 重庆第二师范学院 | A kind of photochemical catalyst Cu3VS4Preparation method |
| CN109599560A (en) * | 2018-12-11 | 2019-04-09 | 广东工业大学 | Four vanadic sulfide anode material of lithium-ion batteries of one kind and preparation method thereof |
| CN109775759A (en) * | 2019-01-10 | 2019-05-21 | 广东工业大学 | A kind of vanadium dioxide anode material of lithium-ion battery and preparation method thereof |
| CN109761277A (en) * | 2019-01-17 | 2019-05-17 | 广东工业大学 | One kind five aoxidizes three vanadium negative electrode materials, preparation method and applications |
| CN113912023A (en) * | 2021-10-08 | 2022-01-11 | 常熟理工学院 | Preparation method of sodium ion battery negative electrode material |
Non-Patent Citations (1)
| Title |
|---|
| 赵艳红.《石墨烯与过渡金属氧化物复合材料制备》.哈尔滨：哈尔滨工业大学出版社,2021,(第第1版版),第11页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114551868A (en) | 2022-05-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Huang et al. | Recent progress of rechargeable batteries using mild aqueous electrolytes | |
| CN110289416B (en) | Preparation method of bismuth-molybdenum bimetallic sulfide as negative electrode material of sodium-ion battery | |
| CN112242526B (en) | Mo-doped VS4 magnesium ion battery positive electrode material | |
| JP2023507209A (en) | Method for preparing high-density aluminum-doped cobalt oxide | |
| Yang et al. | Rocking-chair proton battery based on a low-cost “water in salt” electrolyte | |
| CN114212826A (en) | MnO doped with Mo metal2Electrode material and preparation method and application thereof | |
| CN112038589A (en) | High energy density aluminum secondary battery, positive electrode material thereof and preparation method | |
| CN109775759B (en) | Vanadium dioxide sodium ion battery negative electrode material and preparation method thereof | |
| CN113097464A (en) | ZnS-SnS @3DC composite material and preparation method and application thereof | |
| CN105742596A (en) | Preparation method for positive electrode material of lithium ion battery | |
| Söllinger et al. | Modified H2V3O8 to enhance the electrochemical performance for li‐ion insertion: the influence of prelithiation and mo‐substitution | |
| CN114551868B (en) | Negative electrode material of sodium ion battery and preparation method thereof | |
| CN112103482A (en) | Rare earth metal or transition metal doped lithium titanium phosphate/carbon composite material and preparation method and application thereof | |
| CN111916703A (en) | In-situ synthesis method of lithium iron manganese phosphate/carbon @ graphene composite material | |
| CN115498183A (en) | Modified vanadium manganese sodium phosphate cathode material, preparation and application thereof | |
| CN115312732A (en) | Low-cost alkaline secondary battery positive electrode material and preparation method and application thereof | |
| CN114639813B (en) | Vanadium B-site doped pyrochlore type poly (antimonic acid) material and preparation method and application thereof | |
| CN108615613A (en) | MoP@C nano lines and its preparation method and application | |
| Yan et al. | Hollow heterostructured Cu 1.96 S/NiS microspheres coupled with nitrogen/sulfur dual-doped carbon realizing superior reaction kinetics and sodium storage | |
| CN114655991B (en) | Modified sodium manganate material and preparation method and application thereof | |
| CN110137458B (en) | FTO (fluorine-doped tin oxide) coated modified cathode material and preparation method thereof | |
| Li et al. | Influence of Polyvinyl Pyrrolidone (PVP) on Vanadium-based Compound Composite Performances for Aqueous Zinc-Ion Batteries | |
| CN117810387A (en) | Electrode material, preparation method and application thereof, and alkali metal battery | |
| Bai et al. | Aqueous rechargeable ammonium ion batteries based on MoS 2/MXene with a ball-flower morphology as an anode and NH 4 V 4 O 10 with a layered structure as a cathode | |
| CN115275173A (en) | Zn 3 V 3 O 8 /VO 2 Composite material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |